Insecticides for use as tree spray



July 5, 1960 B. L. ARCHER INSECTICIDES FOR USE AS TREE SPRAY Filed March26. 1957 A TTORNEVS presence of a solid contact catalyst.

2,943,973 lsEfIemE's non 'USE As Tn n SPRAY Bradford L., Archer, Borger,Tex., assigner to Phillips Petroleum Company, a corporation of Delaware'Filed Mar. 26, 1957, ser. N6. 648,710 s Claims. (el. 167-22) Thisinvention relates to novel pesticidal compositions. More specifically,this invention relates to `improvements in .the control of insects,fungi, mites, and other plant pests and to improvements in the k'generaleffectiveness of pesticidal compositions. In accordance with one aspect,this invention provides improved pesticidal compositions to which havebeen imparted specific miticidal activity and an improved method .forcontrolling or eliminating mites, such as red spider mites, European redmites, and 'citrus mites, by way of example. In accordance with anotheraspect, this invention relates to improved pesticidal compositionscontaining as the active principal ingredient thereof a normally wasteproduct lwhich results from the production "of alkyl mercaptans throughthe interaction of hydrogen suliide and selected oleins in the -lnaccordance with amore specific aspect, this invention relates toimproved I'pesticidal compositions for use as a plant spray containing'as Vthe activeV principal ingredient thcreoiE the kettle product whichresults''om Ithe production o'high-boiling alkyl mercaptans through theinteraction of hydrogenV sulflide and selected olens in the .presenceof'a solid con tactvcatalyst.

One of the major defects of many of the currently 'available'pesticides'is-that, in spite of their general effectivehess, they Yarespeciiically without action or have very slight action against-mites,-for example, 'and other mem- -bers of the class 'Arachnida Also, in theart of controlling pests, the agents usedmustnot only -b'e elective inkilling .the pests or rendering them inactive but also must be withoutphytotcxic actionon the-host plants. This is very important since manycompounds'have been Atested Vand found effective against pests but .theyalso ex- -hibitherbicidal activity. Such materials are of no eco- `nomicvalue since the prime purpose in destroying the npest is to preserve thehost.

-An object of this invention is to provide improved pesticidalcompositions. Another object of this invention is to providecompositions which are simple to use but are highly elective against.the various pests, such as insects, mites, and tungi, which destroyplant life. Another object of this invention is to provide improvedpesticidal compositions useful as tree sprays. Another object of thisinvention is to provide improved spray compositions which are highlyeffective against theEuropean red mite, ('Pfatetranychzls piloszs), redspider mite (Tetanychus 'felrarusL- citrus red mite.(Parzrtetravnychzlsctri), and the t like. VAnother object of thisinvention Vis to provide an improvedmethod for controlling oreliminating mites,

1such a'sred spider mites, European red mites, citrus mites,

'andthe like. Other aspects, objects, as well* as the several-advantages#of this invention are apparent from a 'study oft-the disclosure, thedrawing Vand `the appended .pesticidalcompositions by dispersing asmallproportion of a high-boiling sulfur-containing product which results2,943,973' iatented July 5, 1.960

2 from the productionof alkyl mercaptans through the interaction ofhydrogen sulide and selected olelins, preferably, `in the presence of asolid contact catalyst, in a carrier medium, such as an aqueous solutionto form a stable emulsion of the sulfur-containing product therein. Morespecically, in accordance with the present invention, I provide aneiective emulsion spray yfor both deciduous and evergreen-typeplantings, as well as citrus trees, having excellentpesticidal activity,containing as the active principal ingredient thereof the kettleproduct, which is normally a waste material, which results vfrom theproduction of high-boiling alkyl :mercaptans through the interaction ofhydrogen sultide and selected olens in the presence of a solid contactcatalyst.

In accordance with one specific embodiment of the present invention, Iprovide an eiiective emulsion spray having excellent pesticidal activityfor protecting both deciduous and evergreen-type plantings, `as well ascitrus trees, against mites, insects, and fungi, by way of example,containing as the active principal 4ingredient thereof the -kettlebottoms product obtained during the synthesis of tert. dodecylrnercaptan (Sulfole) by the interaction of selected olens, especially, atraction comprised mainly of C12 olens having principally the tertiaryconfiguration, and hydrogen suliide in the presence of a solid contactcatalyst, such as, for example, the ordinarily solid adsorbent-typecatalysts, such as natural or activated clays,` silica gel, charcoal,and the metallic sultides.

rIhe physical properties of this material as well as mercaptan and totalsulfur content and molecular weight are shown in the specific example.The boiling range, mercaptan content, and total sulfur content indicatethat the principal active ingredient of the present invention is amixture of dodecyl mercaptan and heavy dialkyl The distillation range ofthe kettle product ranges from about 166 to about 378 F. at 1 mm. Hgdistillation pressure. Analyses of the ykettle product in'- dioate thatit is'comprised of `a mixture of tertiary dodecyl mercaptan and heavydialkyl suldes. The heavy sulde's are believed to be comprised of amixture of didodecyl disuliide together with other dialkyl mono, diandpolysuhides in'small amounts. i have found that an oil emulsion spraycomprising as the active ingredient .thereof the mercaptan tower kettleproduct obtained'during the synthesis of tertiary dodecyl mercaptanexhibits excellent activity for .the control of the mites, insects, andfungi attacking Iboth deciduous and evergreen-type plants, and there waslittle or no 'apparent damage by the emulsion spray to lthe plantfoliage. The etiectiveness of the spray for the .control :of theEuropean red mite on Chinese ehn trees was found, during .these tests,to be almost spectacular.

The normally waste mercaptan tower kettle product employed in thepractice of my invention, which is obtained during the synthesis oftertiary dodecyl mercaptan, imparts speciiic'pesticidal activity whendispersed in aqueous solutions. The extender that is used is 'preferablyWater. When dispersed in Van aqueous solution, two

suspending, `wetting or"emulsifying agents, such as an alkylated arylpolyether alcohol (Triton X-lGO) and a sodium salt fo' an alkyl arylpolyether sulfate (Triton X-SOl) are' advantageously'employed.Substantially any emulsier or surfactant may be used to hold the dodecylmercaptan tower kettle product in suspension although the two4aoove-df-scribed emulsifying agents are particularly effective and thisis an important feature or" the presen-t invention. One of theemulsifying agents that l use-exhibits an ainity for oil, While theother exhibits an affinity for Water. The pesticidal concentrate,preferably contains from about 3 percent to about 15 percent by weightof surfactants based on the total weight of the concentrate. In thepractice of the present invention,

{,kettle product. e

f V-tiu1s1:n'a yjbecarriedoutY as diminished 'pressure operatheratiol-ofrf'llriton X-'lOO typev to X-V301 typesurfactant, i l forexample, is not Ycri-tical and ratio'swithin. theV range of '1:1 up to10:1. may be advantageously employed toV producegstable emulsions. D f

`fI`ypicalranges of the ingredients Ythat`I can-uscito preparefaconcentrate according to: the .invention com- Y, u *j f Y 2,948,973

' tions a'sordinarily carriedrout with vacuum pumprs'or "prises Yabout600 Ygrams offtertiary dodecyl mercaptan tower'kettl'eproducn 25--100grams `Triton X410() typev fs'urfactant550 grams Triton /X-3OL type`surfactant, -rand'suicient water to make a'total volume of oneY quartconcentrate, usually approximately D-200 grams. A concentrate of thepresent invention may contain as muchas 70, or more, weight percent oftertiary-dodecyl'KV mercaptan tower kettle product. A very eectiveconcentrate that I have prepared 'and used according vto the Y YV'present invention comprisedV 600grams offkettle prod- Y uct, 28Ygrams'Triton X-*lOOV type sulfactant, .7* grams Triton VX-301 typevsurfactant and sufficient water to f vmake a total volume of one quartof concentrate, which required approximately 2,00 grams water.l Thestrength fof the spray that can be employed according to the presentinventionmay varyA considerably and a summer strengthrrecipe, that Iused on Chinese ehn trees, for

"example, to eiectively combat the European red mite, Y'for example, wasmade up by adding one quart of the concentratie to 150 gallons of water;however, when using Athe spray Vof the present invention on trees orshrubs 'in the dormantstate, a spray strength of as much as 10, or'more,timesV as strong as the summer strengthV recipe can be safely andadvantageously employed. Therefore, the proportion of pesticidal agent,i.e., merf captan tower kettle product, employed in the compositions ofmy invention is Vvery small, ofthe orderof about 0.1 toil, or more,Weight percent, depending upon the strength of thespray solutionemployed. The mercaptan tower kettle product containing solutions of,the present invention may be Vapplied in the conventionalywayV as byspraying. The spray composition ofthe presentimiention Ymay alsocontain'other miticidal, insecticidal,and

`fungicidal agents, ifdesired; Q

f YThe Ydodecyl mercaptanii kettle tower*V product Yusi'e'rd in I othermaterial, especially product and kettle product fromv unreacted olefin'Vand.

solvent extraction, may be ern-Y Y ployedifdesired. f' Y Y Y e t Abetter understanding of the present inventionmay be obtaineduponreference to theraccompa'nying sche-V matic flow diagram Vshowing agenerally preferredmethodV of producing and recovering Ythe Vmei-,captantower kettle product employedV in the pesticidal` compositionsY 'ofthepresent invention. Y Y

Hydrogen sulfide introducedby lline'j 1,0, olefinA j stock via line 11,Yand recycle lolelin ,viaVV line 12 are passed through line 13 intopreheater 14 to preheatthe feed material` tov a temperaturecfiabout 190Fraud then passedthrough conduit 15 and introduced into catawith steam.OtherV methods ofV separatngfmercaptan r' 'l lyst case .16. The olen.feed vstockV introduced through Y` conduit 11 was obtained. from thepolymerization of propylene and is that portion of the Ypolymeriproductwhich is recovered in the range Vof about 345 F. j;to; Y

Yabout 370 F., which isf comprised mainly oftertiary 1G12' olens. ThecatalystY preferably employed in catalyst Y Y,chamber 16 is FiltrolGrade 71. Y The temperature ,noi-

Y mally employed in the catalyst chamber utilizing the pre- Y'Vthe"present*invention may beV prepared Vby the methods Y disclosed inU.S.Ipatentfof `Walter AKSchulze, No.

V2,426,646, dated September 2, 1947, and Patent 2,392,555,

clatedY/Jarmar'y 8, V19746, and U.S. patent of Paul P;Warner,"No..2,592,089, dated ApriluS, 1952;VV Y The kettle productutilized in the practice of the presprence' of a suitable catalyst. Theolefin feed stock 'preferably utilized Yis obtained from` thepolymerization VofrpropyleneiandA is that portion of the polymerproductPure hydrogen sulide,V

' "operatedrat a'temperature of about 256' Baudet-f5V Hgrpressureabsolute, to removeunreactedolen -overhead Vthroughy line 29. Theunreacted oleii'niswre'.-

Y ent invention is preferablyiproduced during the synthesis Y Yoftertiary dodecyl mercaptans (sulfolelby the interaction1ofy selectedolensV and hydrogen sulfide inthe Y zremainder removed ,through line 29and recycled-ftoj 'Y ypally a clay-type material commonlyV utilizedasjan ad-j Y sorbent.

prises astabilizatien'operation forthe recovery of un- Hre'actedYhydrogen sulfide, a Ystripping operation for'the removaloffunreactedolen and/or Vhydrocarbon im- Lpurities andfinally a flash'distillationVof'mercaptan and However, 'other types ,of solid.' contact-typecatalysts VVthat can be employed include r'net'allic,sul'rides,V f Yfnllers earth,j silica gel,AV charcoal; t andY the like. The ,Y processof recovering the high-boiling mercaptans and lthe desired'kettleproduct from the catalyst effluent corngf Ythe 'tower-valine 36, landfhfegremaiuder bei 'through 'cooler''h V'a part being Vreintrro ducednt,

Stripping and Vllash distillation operaf -ferred catalyst ranges fromabout 230 F: toY 250 while the pressure employed in the catalyst case is.about 800 p.s.i.g. 'I'he reaction mixture removed from catalyst case16'is passed through conduit 17 and introduced into high pressurestripper 18, wherein hydrogensuldeisV removed overhead via line V19.VHigh pressure stripper V18 is preferably operated at a temperatlu'eslightly above the reaction temperature utilized rin catalyst case 16,preferably of the order'of about 245 F. to about 255 Y F., and at apressure of about 43 p.s.i.g. The reactionAV Y Y Y. product, which ispartiallyndenuded of H28, is Yremoved from high pressure .stripper 18through conduit '20',a'nd

passed Vto low pressure stripper21,whichZ is Yoperatedat a temperatureof about 235 y F.Y andat'atmospheric pressure, to further'remove anyunreactedlHzS ren'laii-V 'ing in'thevreaction mixture, whichis removedoverhead Vvia line Z2. Thev HS denuded reaction product iscre-VVV movedfrom low pressureV stripperlZl throughconduit Y 23` and passed topolymerftower. 24;'whichv isprefer'ably` moved directly from tower 24through conduit '25j'a'nd .part of it recycled to the lower portion oftower24 Y YVthrough line 26, Vand the Yremainder of Vthe unreactedfolefln removed from tower 24 is passedftliroug'hicoler;V (27 and partof the cooled unreacted olefin returned to -the upper portion Yof tower24 through line '28"and: theVv Ytheycatalys't case 16. The olefin-freemercaptanisre- -movedfrom polymer` tower 24 through line 30,Y afpart of'this material'being-recycled to towera24 'through 1 i Vbeater. 31 andconduitY 32, and Ythe remainder of ithe olen-free mercaptan is passedthrough `Vline33;tothe 1j merc'aptan recovery tower V34. Themercaptanftowei ifs Y. Vso

preferably operated Yat Va temperature of abo'fiitf2g72n l. Y 'and 3mm.Hg absolute pressure, YtoY separaterthT dodecyl i Ymercaptan overheadproduct'from the heayyf hig Zltettle product material.. The YdodecylYrrrierfcap't uct is removed'from tower VV34 throughrgline of theinercaptanV being recycledi-tosthe"l,v

tower through linefFtS,4 and the remainderof them ,A p tan,productremoved overhead via-.liner39. FThe,.heayy `high-broilingjkettleproductris removed from t.he, r.1`1ercap'yY tan tower through line 40, apart being recycled' throughV -heater 41 and .conduit 42 and introducedVbackinto tower Y '34, Vwhile the remainderof the kettle 'material'isf'r'e g movedthrough 'conduit 4@ as .theheavy kettle product,

C- It) which I use as the principal activepesticidal ingredientof myinvention.

The inal'product recovered overhead through line 39, the dodecylmercaptan, had the following characteristics:

Purity 95 Weight percent minimum. Weight percent mercapl tan sulfur 1 5weight percent minimum. Molecular weigh t 200i4. API gravity 31.1 to34.0. 5 Hg distillation-- 179 F. minimum, 225 F.

maximum.

The heavy high-boiling kettle productvrecovered in line 43 in one runhad the following characteristics:

I n another run the high-boiling kettle pred-uct had the followingcharacteristics:

Refractive index, ZO/D; 1.4851 Specific gravity, 20/20 0.8965 Mercaptansulfur, wt. percent 3.87 Total Vsulfur Wt. percent 14.82 Molecularweicht` 320 1 mm. Hg distillation, degrees F.:

' IBI" j 166 5% 184 198 20% 228 Y90% 37.8 95% Y (1)V 1Cracked. l

The physical properties of the kettle product will depend in part uponthe relative proportion of mercaptan and dialkyl sulfides containedtherein. Broadly, the mercaptan content of this materialY usually`ranges from about 20 to about 60 percent by Weight, the remainder ccinsistingv essentially of dialkyl suliides', chieliy dialkyldisuliides, as mentioned hereinabove.

Therelative proportions of. mercaptn to dialkyl suldesin the kettleproduct lwill depend uponthe reac tion conditions employed in themercaptan synthesis step andmpon the operatingconditions'in themercaptan tower34. Thus, the proportion Vofmercaptan in the synthesisproduct becomes less, and that of the high boiling dialkyl suldesgreater, as the temperature in catalyst chamber 16 is increased.Also/the extent t0 which the removal of mercaptan productv from kettleseparating eiiiciency of the tower and the conditions of temperature andpressure employed therein.

VOlelin feedstock's, other than the C12 oleiins described hereinabove,whichcan be used in the preparationA ofv the` high-boiling kettleproduct of my invention, include those having from about 8 to about 20carbon atoms per molecule, although oleiins outside this range can b eused. Olens having from about l2 to about 16 carbon atoms are presentlypreferred. The olefins can be normal (straight chain) oleiins or theycan be of the branched configuration, and the double bond can be in anyposition in the molecule.

The usefulness of the new compositions of my inven- Y tion and of thegeneral method of applicationwillbe illustrated in the followingexamples:

Example l A concentrated spray solution was prepared. by mixingtogether' the following ingredients:

1Amount needed to make' total volume of 1 quart (200).

The Triton X- type and Triton X-301 type surfactants are manufactured byRohm and Haas and were added to stabilize the oil-in-water typeemulsion.

The mercaptan kettle product utilized in the concentrated spray solutionwas produced, as previously described with the accompanying ow diagram,i.e., during the synthesis of dodecyl mercaptans from C12 olens havingprincipally the tertiary configuration, obtained asv a portion of theproduct recovered in the range of about 345 F. to about 370 F. from a C3polymerization process, and H28 in the presence of Filtrol Grade 71catalyst. and carried out Within the temperature range of about 230 F.to about 250 F. and at about 800 p.s.i.g. pres-` sure.

employed werel as follows:

1 Cracked--distillation discontinued.

Diluted spray solution tobe used on the treeswas` prepared by addingonequart of the above-concentrated: composition to gallons of water. Thediluted spray',- solution contained about 0.1 weight percent mercaptantower kettle product.

Chinese elmy trees badly infected with European redmites were sprayedduring the summer months, butonly after a considerable amount of damagehad been intlicted to the leaves by the mites, with the above-de-Vscribed diluted solution. The solution was sprayed on Characteristics ofthemercaptan tower kettle product the trees until the solution drippedoV the leaves. vVery few'of 'the mites 'were able tomigrate to newleaves, in-Y dicating thatfahigh kdegree of Vcontrol was obtained.Approximatelyj'thfree Lweeks afterrthe spraying,1it ,was observedthat'bright green Yleaves appeared on .the'ends of the fronds; showingthat healthy new growth had ocurred after Vthe spray had'taken effect.There'was little or uci` apparentdama'geto theplant foliage by the sprayemployed; Also, the trees atthistmel weresubstantially Vfree ofthe redmites.

`Other Chinese elm trees, which had not been sprayed by theV compositionof the present Yinvention, were attacked nthe middle of the'summer withEuropean red and lost VYall or nearly all their'leaves within a lperiodof aboutsitxV weeks, indicating the degree of in# festation of thetrees. A t t Y' Thus, it can be seen from theabove example that thespray composition of the present invention is particularly Vvaluable'inits cmbination'ofpesticidal activity Without Y' rhyfstsxeasfionyf" t Y'Entmple Y A tree spray solution was prepared as in Example I and was eldtested on both deciduous and evergreen-- type plantings infested with-redspider mites and other mitesattacking the plants, and it wasobserved that there wa'slittle or no apparent damage to the plantfoliageby the spray. A1so,tvery few'rofthe insects were able to v migrate tonew leaves, indicating that'a high, degree vof control wasobtained. 1,.v

The pesticidal composition of the present invention is particularlyVvaluable in its combination of miticidal activity without phytotoxic`actiongas demonstrated by the Y above example. Y

. Y Y tExz/znpla*lillV Y* Y* A spray solution prepared las; inl ExampleI wasfapplied'to Amur 4privet (South) plants which were infestedparentinjurytotherplants.`

yln additiontto the speciiichexatnples given rabovejthe;

compositins'foffniy" invention Vare useful in the control of'many otherpests. 'Thus, theyffcan be used against aphids; powdervmldew,Arustsganrl.other;uestsi Y :'As'wllY beterideutlathose Skilledin'theart,varius modifications ot `this inventiontcan ubef made'or followed Vinlthe light ojfjgheforegoing disclosure'V and discussion v.ithoutdeparting .from thespirit for scope-f the diS- closure or the scope ofthe appendedclaims. Y j t 1 .'15.Y A method,or..cgutrpllingsplalrtinsetswhich 190mprises applying.taplantsinfestedwilhsaid insects aninsecticidal amountpf a dispersion 0f a. high-boiling Qr- Y garlicmiur-.Containing naturally wastetmaferial having a total sulfurcontenter Ynot morethan weightrper cent andaY marsepein .Content Qfappr0aimate1y 50` weight percent Said .salive Content Qomprising. a'Vmixture Qt. tertiary, @federalliteraturas` and Abrews k.alkyl Sulds,Said heaYy. siliisesomprisng ,principally Ysii-dodecyl disulde, in.asaque0l1s-arfief medium Ywhich contains from laboiJtQSl o about 151weightlpercent of anjemulsiprepared by` the Vinteraction fof-anoletinhydrocarbon fraction having'a boilingfra'nge of about 345 F.V toVabout lyst within a' temperature range of about 230 F.- to about VY250.F..and'at"about 800 'p.s.i.g. pressure, and fraction.- allydistilling'thel'reaction product `fromsaid processi?! recoversaidbgh-boiling sulfur-containing materialasly kettle product for use inthe method. A f

2. Atmethod of controlling mitesk which omp'ijs'esP piying te plaatsinfestedwith@salaires,y miticiaalampunt amount of an Yaqueoussprayvtwhich 'comprises a mixture Ycontaining as the principal activeingredientthereof Vaf' high molecularV weight lorgar'licsulfur-containingl material having a sulfur content Vof about l5"weightpercent andV Y pests. The' trees Ywere jsprayedjwith the'jdiluteYsolutionV until the solution dripped ott the leaves. 'Y The spraycon-Vtrolled the redrspider mites, yas well as the European redproduct.vv A v-g 35A method?V of protecting aplant'against ,attaekrby of a dispersionofahigh'boiling organic sulfur-containingY kettle product materialhaving a total sulfuncontentjof f not more than 15 weght'percentandadodecylmercaptan' content of about'SV 3 weight percent, Yin anaqueotlscarrier Y medium containing an emulsifying agent,j saidsulfur-confV taining kettle product material having beenV prepared 'bythe interactionof a tertiary C12 olefin hydrocarbon-con;VV`

taining fraction boiling within the range of about 345 F. and,370 F. andYhydrogen sulide in the presence of a solid clay-type contact catalystwithin attemperature range of about 230 F. to 250 F.and'at about800'p.s`.i.g.VV pressure, and fractionally distilling the reactionproductl forfuse Vin the ethod to recover said Vhigh-boilingV kettleYmites which Ycomprises"applyingto said plant, amiticidal a mercaptaucontent of about 50 weight percent, Vsaid material having beenrecoveredasV the Vkettle product re- Y sulting from the'intcraction of a tertiaryCl'z olen hydrot Y carbon-containing fractio'n'b'oiling' not lower thanabout i 4'.Y An insecticidal' Vcompositionrfor use as a plant spray YYboiling organic sulfur-containing kettle product material having atotalsulfur content of not more than 15 weightvv percent, and a dodecylmercaptan content of about 53 weightY percent, said sulfur-containingkettle :producttmaterial' having been prepared *byV the Yinteraction of4a tertiary l C12 olen hydrocarbon fraction boilingwithin the range' ofabout 345 -F..and 370 F. and hydrogen-sulfdein thefpresence of a solidclay-type'fcontact catalyst within Y a temperature range of about1230Fitof 250 ,;F. ,and at about 800 p.s.i.g.rpre'ssure, and fractionallydistilling the reactionrproduct for use -inftheV compositiongto, recoversaid high-boiling'kettle product.

5; A composition effective for the killing of plantpests Y whichcomprises aV mixtureoffa highV molecular weight l Yorganicsulfur-containing .materialzcomprised. of vabout 370"Y Yl'fandcomprisedr-principallyfiofolens having; t l Yfrom aboutV 8.to`20 carbon.atoms iper molecule and hy-Y 'drogen'fasuldefn'jthe presence of a solidclay-typeicataequal parts of tertiarydodecyl Amercaptanand Vheavydialkyl sultdes, said material having been recovered'as 0.1

to1 VWeightv percent of the kettle product resulting fromv n 'theinteraction of Ya Cm-tertiaryolen hydrocarbontrac VY tion boiling intherange of about 345 9 Ffto about 370 F; Y

and HZSin Athe presence of aisolid contact catalystat a temperaturewithin range of 230 F. to 250 Fr, atabout 800 -p.s.i.g. pressure, and anaqueous liquid carried medium Ycontaining an emulsifying agent;V Y

l VYReferences Citedrin the tile of this/'patent -Y Y 1,UNITED'SlATESPATENTS '1,986,213j Remyr 1 ;Jan. V.1, 1935V

2. A METHOD OF CONTROLLING MITES WHICH COMPRISES APPLYING TO PLANTSINFESTED WITH SAID MITES, A MITICIDAL AMOUNT OF A DISPERSION OF AHIGH-BOILING ORGANIC SULFUR-CONTAINING KETTLE PRODUCT MATERIAL HAVING ATOTAL SULFUR CONTENT OF NOT MORE THAN 15 WEIGHT PERCENT AND A DOCECYLMERCAPTAN CONTENT OF ABOUT 53 WEIGHT PERCENT, IN AN AQUEOUS CARRIERMEDIUM CONTAINING AN EMULSIFYING AGENT, SAID SULF-CONTAINING KETTLEPRODUCT MATERIAL HAVING BEEN PREPARED BY THE INTERACTION OF A TERTIARYC12 OLEFIN HYDROCARBON-CON TAINING FRACTION BOILING WITHIN THE RANGE OFABOUT 345* F. AND 370* F. AND HYDROGEN SULFIDE IN THE PRESENCE OF ASOLID CLAY-TYPE CONTACT CATALYST WITHIN A TEMPERATURE RANGE OF ABOUT230* F. TO 250* F. AND AT ABOUT 800 P.S.I.G. PRESSURE, AND FRACTIONALLYDISTILLING THE REACTION PRODUCT FOR USE IN THE METHOD TO RECOVER SAIDHIGH-BOILING KETTLE PRODUCT.